Preparation of sulphonated polyketones

ABSTRACT

Sulphonated polyketones are prepared by reacting a linear alternating copolymer of carbon monoxide and one or more olefins (polyketone) with a sulphonating agent (e.g. chlorosulphoric acid) in a solvent (e.g. dichloromethane) at a temperature in the range -20° to +40° C. A molar excess of sulphonating agent is preferably used. The sulphonated polyketone produced contains one or more types of unit of formula--[COC(R 1 ) 2  C(R 1 ) 2  ]--wherein the R 1  groups are independently H, C 1  to C 10  alkyl or SO 3  H with the proviso that at least one R 1  group is SO 3  H.

This application is a division of application Ser. No. 07/581,026 filed on Sep. 12, 1990, now U.S. Pat. No. 5,153,280.

The present invention relates to a class of new polymers called sulphonated polyketones and processes for their preparation.

EP 121965 and EP 213671 discloses a class of polymers, hereafter called polyketones, which can be synthesised by the action of carbon monoxide on alkene(s) in an alcohol in the presence of a palladium catalyst, a chelate phosphine and an anion of an acid having a pKa less than two. The polyketones produced are linear alternating copolymers of carbon monoxide and the alkene(s) employed.

It has now been found that polyketones of the type disclosed in EP 121965 and EP 213671 may be modified by sulphonation and that the resulting sulphonated polyketones are strongly acidic solids useful as acidic catalysts in for example homogeneous and heterogenous catalytic processes.

Accordingly the present invention comprises a polymer of one or more types of unit of the general formula: ##STR1## where the R¹ groups are independently selected from H or C₁ to C₁₀ alkyl or SO₃ H with the proviso that at least one R¹ group is SO₃ H. It is preferred that those R¹ groups which are not SO₃ H are selected from H or C₁ to C₄ alkyl, most preferably H or methyl.

The new polymers are stable and the SO₃ H groups are strongly acidic as a result of the electron withdrawing power of the ketone functionality.

Whilst the polymer of the present invention may consist exclusively of units of the general formula given above it is envisaged that the polymer may also contain other units. In particular, since the polymer has been produced by sulphonation of a corresponding polyketone, the polymer may also contain one or more types of unit having the formula: ##STR2## wherein the R¹ groups are independently selected from H or C₁ to C₁₀ alkyl only.

It will also be appreciated that the polymer may also be comprised of one or more unit of the general formula: ##STR3## due to dehydration of the polyketone. In this formula the R¹ groups are independently selected from H, C₁ to C₁₀ alkyl or SO₃ H.

The polymer is preferably comprised of 15-100% by weight of units of formula (I).

The polymer defined above can be prepared by a process which comprises the step of sulphonating a corresponding polyketone comprised of one or more types of unit of formula II. Typical processes for effecting such a sulphonation are described in the textbook "Sulphonation and Related Reactions" by E. E. Gilbert, Interscience Publishers, N.Y., 1965. A particularly good method of sulphonation consists of reacting a slurry of the polyketone with a sulphonating agent in the presence of a solvent. The preferred solvents are halogenated solvents e.g. dichloroethane and glacial acetic acid, with dichloroethane being most preferred. Preferably the process is carried out at a temperature in the range -20° to +40° C., most preferably -5° to +5° C. Suitable sulphonating agents include chlorosulphonic acid, concentrated sulphuric acid, pyridine/sulphur trioxide, 2,6-lutidine/sulphur trioxide and mixtures of chlorosulphonic acid with concentrated sulphuric acid, dimethyl formamide, 1,4-dioxane or triethyl phosphate. The most preferred sulphonating agent is chlorosulphonic acid. It is preferred that the sulphonating agent is used in a molar excess over the polyketone.

The new polymers are chemically reactive and can be used as precursors for further chemical transformations. An example is the preparation of thiol containing polymers by reacting the sulphonated polyketone with PCl₅ and subsequent reduction. The product is a thiol polymer of one or more types of unit of the general formula: ##STR4## where R¹ can be independently selected from H or C₁ to C₁₀ alkyl or SH with the proviso that at least one R¹ is SH. Such thiol polymers may of course also contain one or more types of unit having formulae analogous to the formulae (I)-(III) given above. Such thiol containing polymers can be used inter alia as ion-exchange resins.

By virtue of their strongly acidic properties, the sulphonated polyketones of the present invention are also useful catalysts for processes which require an acid catalyst. An example of such a process is esterification wherein a carboxylic acid, typically a C₁ to C₁₀ aliphatic carboxylic acid is reacted with an alcohol, typically a C₁ to C₁₀ aliphatic alcohol to produce the corresponding ester.

According to the present invention there is therefore provided a process for the preparation of an ester whose process comprises reacting a carboxylic acid with an alcohol in the presence of a sulphonated polyketone as described above.

The sulphonated polyketones of the present invention are also effective as agents for removing ammonia or amines from solution. This is particularly advantageous when the medium containing ammonia or amines does not dissolve the sulphonated polyketone. Thus a solution of ammonia or amine in such a medium can be pumped or otherwise drawn through a bed of the sulphonated polyketone at a rate sufficient to effect complete removal from the medium of the ammonia or amines.

The following examples illustrate the invention.

EXAMPLE 1

A slurry of an ethene/CO copolymer (4 g) (prepared according to EP 121965) in 70 ml of dichloroethane was prepared and cooled to 0° C. A solution of ClSO₃ H (5.3 ml) in 30 ml of dichloroethane was then added to the slurry, with stirring, over a period of fifteen minutes. The resulting mixture was stirred for a further thirty minutes while the temperature was maintained at 0° C. and then poured into 200 ml of methanol. The resulting product was then filtered, the residue washed twice with water and dried under vacuum. A yield of 5.08 g of a brown granular solid was obtained containing 7.7% by weight of sulphur and 2.95 mmoles g⁻¹ of acid sites. Results from ¹³ C solid state NMR analysis were consistent with known SO₃ H compounds.

EXAMPLE 2

The procedure of Example 1 was repeated using 20% oleum (15.1 ml) as the sulphonating agent. A yield of 6.4 g of a black solid was obtained containing 4.06 mmoles g⁻¹ of acid sites and 10.8% by weight of sulphur.

EXAMPLE 3

The procedure of Example 1 was repeated using concentrated sulphuric acid (10 ml) as the sulphonating agent. A yield of 9.82 g of a black solid was obtained which contained 7.54 mmoles g⁻¹ of acid sites and 14.2% by weight of sulphur.

EXAMPLE 4

The procedure of Example 1 was repeated using glacial aceticacid as the solvent and concentrated sulphuric acid (5 mL) as the sulphonating agent. The experiment was carried out at 16° C. for one hour. The product was filtered and washed twice with dichloroethane. A pale brown solid (4.20 g) was obtained which contained 1.29 mmoles g⁻¹ acid sites and 3.4% by weight of sulphur.

EXAMPLE 5

The procedure of Example 1 was repeated using a mixture of ClSO₃ H (5.3 ml) and DMF (12.2 ml) as the sulphonating agent. After addition, the resulting mixture was warmed to 16° C. and stirred for two hours. A pale brown solid (4.20 g) was obtained which contained 1.29 mmoles g⁻¹ acid sites and 3.4% by weight of sulphur.

EXAMPLE 6

The procedure of Example 1 was repeated using a mixture of ClSO₃ H (5.3 ml) and 1,4-dioxane (13.4 ml) as the sulphonating agent. A dark solid (6.28 g) was obtained containing 2.02 mmoles g⁻¹ of acid sites and 3.5% by weight of sulphur.

EXAMPLE 7

The procedure of Example 1 was repeated using a mixture of ClSO₃ H (5.3 ml) and triethyl phosphate (26.7 ml) as the sulphonating agent. A yield of 4.31 g of polymer was obtained which contained 0.77 mmoles g⁻¹ acid sites and 1.7% by weight of sulphur.

EXAMPLE 8

The procedure of Example 1 was repeated using pyridine-sulphur trioxide (12.5 g) as the sulphonating agent. The temperature was increased to 16° C. and the reaction carried out over twenty four hours. A yield of 4.16 g of polymer was obtained which contained 0.82 mmoles g⁻¹ of acid sites and 0.3% by weight of sulphur.

EXAMPLE 9

The procedure of Example 8 was repeated using 2,6-lutidine-sulphur trioxide (27 g) as the sulphonating agent. A grey solid was obtained (3.68 g) containing 0.23 mmoles g⁻¹ of acid sites and 0.1% by weight of sulphur.

EXAMPLE 10

A sample of an ethene/propene/CO terpolymer (5 g), containing 7 mole % propene in form of beads of 250-600 um diameter, was suspended in 50 ml of dichloroethane. The resulting mixture was cooled to 0° C. A solution of ClSO₃ H (6 ml) in dichloroethane (50 ml) was added, with stirring, over a period of 45 minutes. The beads were then separated by filtration, washed twice with dichloroethane, twice with water and then dried under vacuum. The beads were found to contain 6.9% by weight of sulphur and 3.2 mmoles g⁻¹ of acid sites.

EXAMPLE 11

A sample of the sulphonated polyketone (5 g) prepared as described in Example 1 was suspended in CH₃ CCl₃ (50 ml) containing 4 g of PC1₅. The resulting mixture was stirred at room temperature for three hours. The solution was then filtered and the solid product washed twice with CH₃ CC1₃. The washed product was then suspended in 50 ml of acetic acid and 5 g of zinc powder added to the mixture, with stirring. The reaction was then left for sixteen hours. The resulting mixture was poured into 500 ml water prior to filtration. The product was further treated with 500 ml of 1M HCl and the resulting solution filtered again. A yield of 4.75 g of a thiol-containing product was obtained.

EXAMPLE 12 Esterification of Acetic Acid

A sample of the sulphonated polyketone (100 mg) prepared as described in Example 1 was suspended in a mixture of acetic acid (110 mmole), methanol (110 mmole) and cyclohexane (0.60 g, used as internal standard in gas chromatography). The reaction mixture was stirred at 55° C. for three hours. Samples were extracted at 30 minute intervals and analysed for ester content using gas chromatography.

The reaction was repeated except the sulphonated polyketone was replaced by a commercial sulphonic acid polymer, Amberlyst 15.

The reaction was further repeated in the absence of a catalyst.

The results are shown in FIG. 1.

EXAMPLE 13

A sample of the sulphonated polyketone (2 g) prepared as described in Example 1 was added to a burette as a slurry in 30 ml of methanol. Diethylamine (60 mmole) was added to the burette and allowed to diffuse through the polymer at a rate of 10 bed volumes per hour. The polymer effluent was collected in 5 ml aliquots. Alternate aliquots were titrated with 14 mM HCl to determine amine content, using bromothymol blue as indicator. The results are shown in FIG. 2. 

I claim:
 1. A process for preparing a polymer of one or more units of the formula: ##STR5## wherein the R¹ groups are selected from the group consisting of H, C₁ to C₁₀ alkyl, and SO₃ H with the proviso that at least one R¹ group is SO₃ H, which process comprises the step of reacting a polyketone in a solvent with a sulphonating agent at a temperature in the range -20° to +40° C.
 2. A process as claimed in claim 1 wherein the sulphonating agent is selected from the group consisting of chlorosulphonic acid, concentrated sulphonic acid, pyridine/sulphur trioxide, 2,6-lutidine/sulphur trioxide and mixtures of chlorosulphonic acid with concentrated sulphuric acid, dimethyl-formamide, 1,4-dioxane, and triethyl phosphate.
 3. A process claimed in claim 1 wherein the sulphonating agent is chlorosulphonic acid.
 4. A process as claimed in claim 1 wherein the solvent is dichloroethane. 